Organic nitrogen bases and their salts



"Patent Ap 1938 V I 2,1

UNITED STATES PATENT A OFFICE.

ORGANIC NITROGEN BASES AND THEIR I SALTS Herman A. Bruson, Philadelphia,Pa, assignor to Riihm & Haas Company, Philadelphia, Pa.

No Drawing. Application May 28, 1936, Serial No. 82,183

11 Claims. (CI. 26099.12)

This invention relates to new amines and their In preparing the complexether halide as in salts and to the quaternary ammonium bases andEquation (1) a monohydric phenol is treated with salts derived fromthese amines. It also relates at least an equimolecular quantity of adihalogeno 2 to a process for preparing these new compounds. ether inwhich each of the halogen atoms is at- It relates more particularly tothe water-soluble tached to. a terminal methylene group, in the 6 saltsand bases which have been found to be presence of at least anequimolecular proportion ex ll n w tt n em ifyin per ing and 01 analkali hydroxide. This mixture is heated a n a e ts whi may be nera yass d at about 100 to 140 c. until the reaction is comaS C p y activecompoundsplete. The time of heating may vary from two 7 10 The aminesarerthqse ving the general stru to more than fifteen hours, depending onthe re- 10 6 actants. The temperature at which the reaction is carriedout will also vary somewhat according to the actual materials involved.When the rei which R is a hydrocarbon radical containmg action iscomplete, the alkali halide is filtered 15 an aromatic nucleus at itspoint of attachment produci is usually a mum relatively to the etheroxygen atom, A is an alkylene radical bqlling pomt which y be P d yhaving more than one carbon atom, n is equal to dlstmatlon in vacuoone(1) or zero (0), and N is thenitrogen atom In Order to Prepare the aminequaternary derived from ammonia a primary or Secondary ammonium saltthis halogenated complex ether aliphatic, cycloaliphatic, arylaliphaticor hyis heated with arhmohia the desired p mary. f droxyaliphatic amineor secondary heterocyclic secondary tFrtlal'y amine until the reactionis amine, complete. ThlS usually requires from about one Th amines areny prepared by condensto fifteen or more hours at temperatures ranginging one m l, e h of monohydric phenol and a from about 75 to about 180C. depending on the 25 polyalkylene ether, having a halogen substituentnature and reactivity of the ingredients- The on a h of it te i carbonatoms, in the product is then treated with an alkali hydroxide presenceof an alkaline condensing agent, reacting to Set free the base which ybe Separated from the product thus obtained with ammonia, a pritheaqueous Solution and Purified y di t o mary or secondary amine andtreating the rein vacuo. In many cases reaction products may suitingamine hydrohalide with an alkali or be used directl s nce, s a ts of t eam nes or alkaline earth hydroxide. of the quaternary ammonium bases,they are The reactions involved may be outlined as soluble in water. Thefree base may then be i follows: converted to a salt by treatment withan organic 1 R-OH+ZXA(OA)..OAX+NaOH- ROA(O-A)-O--AX+NaX 35 (2R--OA(OA).0A-X+I|\I 11-0-A 0A ..-0A-1 Ix in which X is a halogen atom.or inorganic acid such as, for example, acetic,

Quaternary ammonium salts corresponding to formic, lactic, acrylic,propionic, crotonic, phosthese amines may be made by treating a tertiaryphoric, sulfuric, hydrochloric, etc. In case it is 45 amine having as asubstituent the radical desired to convert the amine to a quaternary am-I monium compound, it may be treated with an R' OA(OA)" O A alkylatingor aralkylating agent such as benzyl with an alkylating agent such as analkyl chlochloride, dimethyl sulfate, diethyl sulfate, di-

ride, dialkyl sulfate, aralkyl chloride, etc. Altermethyl oxalate,methallyl chloride, methyl iodide, 60

natively the quaternary ammonium salts may be ethyl bromide, methylthiocyanate. benzyl thioobtained by treating a tertiary amine with thecyanate and other similar ones.

I phenolic complex ether chloride. The bases may The phenols which canbe used for the purpose be obtained from these salts by treatment withof this invention include the following: Phenol, caustic. 0-, m-,orp-cresol,thymol,carvacrol,p-ter-butyl- 55 phenol, p-sec-butylphenol,p-ter-amylphenol, p-n-arnylphenol, n-amyl-m-cresol, p-sec-octylphenol,p-ter-octylphenol, p-sec-hexylphenol,

laurylphenol, o-. m-, or p-cylohexylphenol, 0-, m-, or p-phenylphenol,0- or p-benzylphenol, aor p-naphthol, ter-butyl-pZ-naphthol,ter-octylenaphthol, 1,3,5-xylenol, and their obvious equivalents. Themost useful products are those derived from p-alkylated phenols in whichthe alkyl group contains from 4 to 12 carbon atoms inclusive since thesecompounds show the highest degree of capillary activity. The alkyl groupmay be a straight or branched chain.

Among the dihalogeno-polyalkylene ethers which can be used may bementioned p,B'-di chloro-diethyl ether, p,p'-dichloro-diisopropyl ether,dichloro dibutylether, dichlorodiamyl ether, and the correspondingdibromo derivatives, fl-chloroethyl-B-chloroethoxyethyl ether, and theirhigher homologues containing up to 18 carbon atoms.

The compounds used for the amination of the heated for 15 hours on anoil bath at 120435? C. under a reflux condenser while stirring. Thethick brown oil obtained was mixed with 80 cc. of 10% caustic sodasolution, 100 cc. of water and 150 cc. toluene and warmed for one-halfhour on a water bath at 60-70 C. The toluene layer was then separatedand washed with 100 cc. of water. After distillation of the toluene andfractionation of the residual oil in vacuo the p- (a,a,'y,'ytetramethylbutyl) phenoxyethoxyethyldiethanolamine was obtained as apale yellow viscous oil in a yield of 82% of theory. It boiled at255-260 C./5 mm.

This 011 when dissolved in 10% phosphoric acid gave a clear solutionwhich was very foamy, soapy, and lathery when shaken. Such solutions canbe used for wetting out metal surfaces as in the cleaning of steelautomobile bodies with phosphoric acid or for rustproofing steel withmetal phosphate-phosphoric acid solutions.

Example 2 C211: CH2CH2OH mono-halogenopolyalkylene ethers of the phenolsused can be ammonia or primary, secondary and tertiary amines. Typicaluseful amines for the purpose are mono-, di-, or trimethylamine, mono-,di-, or triethylamine, or their higher homologues; monoethanolamine,diethanolamine, dibenzylamine, cyclohexylamine, dicyclohexylamine,piperidine, morpholine, benzyl-dimethylamine, and the like.

' For practical purposes and in view of their cheapness,fifl-dichlorodiethyl ether and p,fl'-dichlor-diisoprcpyl ether arepreferred for illustrating this invention in the following examples.

The invention, however, is not limited to the exact conditions of time,temperature, concentration etc. shown nor to the exact ingredients Asolution of 30 grams of p-(a,a,'y,'y-tetramethylbutyl)phenoxyethoxyethyl diethanolamine in 50 grams of toluene was mixed witha solution of 12.5 grams of diethyl sulfate in 25 grams of toluene, andthe mixture heated for one hour at Bil- C. The clear solution obtainedwas then evaporated under reduced pressure at 40-50 C. to remove thetoluene. The residual quaternary ammonium compound was a viscousamber-colored oil which dissolved readily in water to give a clear,foamy, soapy solution, useful as a wetting-out agent and which wasstable to hard water. The quaternary ammonium base can be liberated bytreatment with alcoholic potassium hydroxide.

Example 3 as it may be otherwise practiced within the scope of theappended claims.

Example 1 CH: CH:

boiling at 1'77-1'78 C./4 mm. was isolated as a colorless oil bydistillation of the filtrate in vacuo.

A mixture of 39 grams of the p-(u,a,'y,'y-tetramethylbutyl)-phenoxyetho'xy-ethyl chloride thus obtained and 26 grams ofdiethanolamine was C Hr-C H:

A mixture of 25 grams of morpholine and 62 grams ofp-(a,u,v,'y-tetramethylbutyl)phenoxyethoxy-ethyl chloride was heatedunder reflux for CHz-CHaOH CHrCHaOH 7 hours at -120 C. The reactionmixture was made alkaline with caustic soda solution, and the oil layerseparated v and washed. Upon fractionating this oil ,in vacuo an 83%yield of p- (a,oz,'y,'y tetramethylbutyl)phenoxyethoxy-ethyl-N-morpholine was obtained as a pale yellow oilboiling at 203-208 C./4 mm.

' It dissolved readily in 10% solutions of lactic,

phosphoric, oxalic, or acetic acids, and these solutions gave heavyfoams when shaken.

Upon treating 36 grams of p-(oz,a,'y,'y-tet1l1- methylbutyl)phenoxyethoxy-ethyl-N -morpholine with 16 grams of diethyl sulfate intoluene as described in Example 2, the corresponding compound fromtechnical diamylamine and p-(,,'1,Y-tetramethylbutyl)phenoxyethoxy-ethyl chloride was obtained. It is aviscous, pale yellow mass which dissolves readily in water to give afoamy,

boiled at 220-240 J6 mm. Its phosphate gave a very foamy solution inwater.

soapy solution. The quaternary ammonium base Example 6 nn ur-onionCII:C-C O-OlIz-CH1OCHz-CHzN\ on, CHr-OHzOH can be liberated by treatmentwith alcoholic barium hydroxide solution.

Example 4 CH3 CH3 form a soap-like, foamy solution.

useful as a spreader for insecticides.

.The quaternary ammonium base is liberated by treatment with alcoholiccaustic soda solution.

Example 5 CH3 CH1 CH3 OH;

This compound was prepared by heating a mixture of 52 grams of p-,(a,a,'-tetramethylbutyl) phenoxyethoxy-ethyl chloride with 25 grams ofdiethylamineunder reflux for 9 hours on a boiling water bath. The basewas liberated with dilute caustic soda solution. It separated as ayellowish oil boiling at 210-220 C./ 10 mm. Upon 31 grams ofdiethanolamine was mixed with 51.5 grams ofp-ter-butylphenoxyethoxy-ethyl chloride, a colorless oil boiling at184-186 C./10

CHE-CH:

CH2CH mm. which was prepared from p-ter-butylphenol,s,p'-dichlorodiethyl ether, and caustic soda, according to the procedureset forth in Example 1. The mixture was heated at 115135 C. for 10 hoursand then made alkaline with 90 cc. of 10% caustic soda solution. Thep-ter-butylphenoxyethoxy-ethyl-diethanolamine separated as an oil whichafter washing and fractionating in vacuo is a. pale yellow oil boilingat 265 C./10 mm.

Yield 71% of theo y.

The acetate, phosphate, and lactate of this base dissolve in water togive foamy solutions having low surface tensions. The quaternaryammonium compounds derived from the above base and diethyl sulfate,,dimethyl sulfate, or benzyl chloride are water-soluble capillary activecompounds.

Example 7 CH3 CH: C H:

CH Cl CH3 A mixture of 2'7 grams of p-ter-amylphenoxyethoxy-ethylchloride and 13.8 grams of trimethylamine was heated in a sealed tube at150-160 C. for 2 hours. The crystalline mass obtained after evaporationof the excess tri- Cali methylamine is the quaternary-ammonium chloridehaving the above formula. Its aqueous solution yields a stable heavyfoam and is useful for fixing direct dyestuffs onthe fibre. Upon treatment with alcoholic potassium hydroxide the quaternary ammoniumhydroxide is formed.

Example 8 treatment with dimethyl sulfate it gave a watersoluble,soap-like body having the formula A mixture of 20.8 grams ofp-ter-butylphenoxyethoxy-ethyl chloride and 11 grams of benzylThe-analogous diamylamine derivative obtained dimethylamine was heatedunder a reflux conternary ammonium hydroxide is formed by treatment withalcoholic sodium hydroxide solution.

as a thick syrup. Its aqueous solution possesses a soap-like characterand is useful for fixing acid dyes on the fibre.

Example 11 A mixture of 32 grams of p-(a,a,'y,'ytetl8. methylbutyl)phenoxyethoxy ethyl-dimethylamine and 12.7 parts of benzyl chloride wasExample 9 warmed to 50 C. with 50 grams of benzene for CH; CHr-CHaOH C11-0HrOO-CH:CHQO-CHr-CH|N (1m oHr-omon 31 grams of diethanolamine wasmixed with 54 grams of p-ter-amylphenoxyethoxy-ethyl chloride, acolorless oil boiling at 153-155 C./3 mm, which was prepared fromp-ter-amyl phenol m3- dichlorodiethyl ether, and caustic soda, accord- 2hours. The benzene was then evaporated. The residual viscous mass gave afoamy, soapy solution in water.

molecularly equivalent quantity of diethyl sulfate as described inExample 2, the p-ter-amylphenoxyethoxyethyl-dihydroxydiethyl-ethylammonium sulfuric ethyl ester.

cam

was obtained. as a pale yellow oil. Its aqueous solution is suitable asa wetting-out agent for cotton yarn.

Example 10 A mixture of 51.5 grams of p-(a,a,' ,'y-tetramethylbutyl)phenol, 11.7 grams of sodium hydroxide, 22 cc. of water and 171 grams of5,5- dichloro-diisopropyl ether was heated at C. with rapid agitationunder a reflux condenser for 9 hours. The product was worked up asinExample 1, yielding 50 grams of teroctylphenoxyisopropoxy-isopropylchloride. (Colorless oil B. P. 190-195" C./5 mm.)

This oil was converted to the tertiary amine salt by heating it withexcess of dimethylamine at -140" C. in an autoclave for 2 hours. Theproduct was treated with excess caustic soda solution and the free baseisolated by distilla- CHg-CHaOII CHr-CHzOH CzHu CH:

A mixture of 1 mol. equivalent of a,a,'y,'ytetramethylbutylphenoxyethoxyethyl chloride and 2 mols (excess) of dimethylamine was heat ed in anautoclave 5 hours at C. The reaction mass was made alkaline with causticsoda solution and the free base isolated by distillation in vacuo afterremoval of unreacted dimetylamine. It was a colorless oil boiling at191-194 C./3 mm.

This oil was heated with a molecularly equivalent quantity of diethylsulfate in dry benzene on a water bath for 1 hour. Upon evaporation ofthe solvent, the ter-octylphenoxyethoxyethyldimethylethyl ammonium ethylsulfate was left soluble quaternary ammonium salt was obtained havingcation active properties. It readily combines with Congo red dye to forman insoluble lake and is useful for improving the fastness to washing ofdirect dyes.

Example 13 CH:

z-GHzOH OCHz-CHz-O-CH:-CILN CH Cl. g 2 OH CH; CH:

41.5 grams of diethanolamine was mixed with 51.5 grams ofthymoxyethoxy-ethyl chloride, a colorless oil boiling at PIS-178 C./ 10mm., which was prepared from thymol, caustic soda. andp,p-dichlorodiethyl ether, according to the procedure set forth inExample 1. The mixture was heated 15 hours at 110-180 C., then madealkaline; and the base which separated as an oil was washed andfractionated in vacuo. The thymoxyethoxy-ethyl-diethanolamine distilledat 233-236 C./5 mm. as a pale yellow oil. Yield 72% of theory.

Its phosphoric acid salt dissolved readily in water to give a foamysolution useful as a wetting agent.

The analogous derivative obtained from xyle-r noiw-ethoxy-ethylchloride, a colorless oil boiling .at' 168 C./10 mm. which was preparedfrom 1,3,5-xylenol, caustic soda and p,fl-dichlorodiethyl etheraccording to the procedure set forth in Example 1, and diethanolamine,was a pale yellow oil boiling at 252 C./ 10 mm., the hydrodiethylamine,piperidine, morpholine, dicyclohexylamine or dibenzylamine in the abovecondensation to obtain the analogous tertiary amines. The water-solublephosphates, lactates, acetates, and quaternary ammonium salts of thesephenol ethers are likewise useful as capillary active compounds.

Example 15 A mixture of 55 grams of p-ter-amylphenoxyethoxy ethylchloride and 7 grams of anhydrous ammonia was heated in an autoclave forthree hours at 160-180 C. The reaction product was then boiled underreflux with excess 10% caustic soda solution, and the oil separated anddistilled.

With diethanolamine and Product obtainedfiwl-lNiaphthoxy)ethyl-W-chloroethyl ether (from fl-naphbenzyi phen B.P. 250-23910 mm.

fi-(o-Be zylphenoxy)ethyl-W-ohloroethyl ether (fromop-(o-Cyclohexylghengxy)ethyl-B chloroethyl other (from one.o-cyclohexyl B. P. 206-209" 10 mm.

8(p-Cyclohexyl hamliirwethyl-W-chloroethyi ether (from p-cyclohexyl onB. P. 2l8 220 10 mm.

(o-Phenylphenoxy)ethyi-fi-chloroethyl ether (from a phenylphenol B. P.211-212l10 min.

lphanoxy)ethyl-E-chloroethyl other (frompfl-Naphthoxyethoxyethyl-dicthanolamine Oil. B. P. 275280/7 mm.

p-Phenylphenoxyethoxyethyl-diethauolamine. (Resinous mass) I WithDibenzylamine and ethyl et er B. P. 177-178/4 mm.

, 'letramethylbutylphenoxy)ethyl-B chloro- (fromp-a,a,7,'y-tetramethylbutylphenol) p Tar octylphenoxyethoxyethyl-N-dibonzylamine (Waxy crystals) chloride of which possesses capillaryactive properties.

Example 14 The water-soluble pentavalent N-derivatives of the abovebases notably their lactates, phosphates, acetates and the quaternaryammonium salts oborb-onion A mixture of 12.3 grams of-,a,-y,'y-tetramethylbutylphenol, 2.7 grams of caustic soda, 5 cc. ofwater and 64 grams of p-chloroethyl-p'-chloroethoxyethyl ether, acolorless oil boiling at 235 C., prepared by treating triethylene glycolin dimethylaniline with thionyl chloride, was heated 5 hours at 110-115C. while stirring under a reflux condenser. The water was then distilledoff, the sodium chloride removed by filtration. and the clear filtratefractionated. Thep(ter-octylphenomethoxy)ethyl-pwhloroethyl etherdistilled as a. colorless oil at l99-20'7 C./3 mm. This was mixed with amolecularly equivalent quantity of diethanolamine and heated 8 hours at120 C. The base was then liberated by treatment with caustic soda. Itsphosphate dissolves readily in water to give a foamy, soapy solution.Upon treatment with diethyl sulfate the water-soluble quaternaryammonium derivativeis formed. Its aqueous solution is useful as awetting-out agent.

In place of the diethanolamine, one can use GH -CHnOH tained with benzylchloride, diethyl sulfate, or dimethyl sulfate are likewise useful ascapillary active agents.

Among the uses suggested for such capillary active compounds is theiremployment as textile assistants in dyeing, bleaching, mercerizing andmordanting operations; as spreaders for insecticides, dispersing agentsfor pigments, as wetting and penetrating agents, pickling inhibitors,and assistants in leather tanning and finishing operations. Thewater-soluble quaternary ammonium salts of the type herein set forth areparticularly useful for rendering dyeings with acid, direct, or chromedyestuffs on rayon, cotton, or on cellulose esters or ethers, faster tolight and washings. For

this purpose the textile is treated with a solutionof the capillaryactive compound and subsequently dyed in the usual manner.

The quaternary ammonium hydroxides are useful as capillary activecompounds in alkaline solution and may be. used as mercerizingassistants.

I claim: 1. A compound of the formula nucleus of the benzene andnaphthalene series, A represents an alkylene radical containing more 2.A compound of the formula 3. A compound of the formula CH3 CH3 H: CH3

than one carbon atom, and a, b, and c are members of the groupconsisting of alkyl, hydroxy- CzHl CHPCHQOH CHg-CHgOH I CzHrO-S O 4. Acompound of the formula in which X is an alkyl radical, a, b, and c aremembers of the group consisting of alkyl, hydroxy alkyl, aralkyl andcycloalkyl radicals, and

.d is an anion.

5. A compound of the formula in which X is an alkyl radical, a, b,'and care members of the group consisting of alkyl, hydroxyalkyl, aralkyl, andcycloalkyl radicals, d is an anion, and n is an integer less than 3.

'7. A compound of the formula l XR(-O-CH2-CH2),.-0CHCHzN\ l c in which Xis an alkyl radical, R is one of the group consisting of benzene andnaphthalene nuclei, a, b, and c are members of the group consisting ofalkyl, hydroxyalkyl, aralkyl and cycloalkyl radicals, d is an anion, andn is an integer less than 3.

8. A compound of the formula a b XR(OA)"OAl I in which X is an alkylradical, R is an aromatic anion, and n is an integer less than 3.

9. A compound of the formula ab l/ R(-O-A),.O-AN

I d c in which R'is an aromatic hydrocarbon radical of the benzene andnaphthalene series nuclearly connected to the ether oxygen atom, Arepresents an alkylene radical having more thanone carbon atom, and a,b, and c are members of the group consisting of alkyl, hydroxyalkyl,aralkyl, and cycloalkyl radicals, d is an anion, and n is an integerless than 3.

10. A compound of the formula 11 b noA ,.o-A-i z d c in which R is ahydrocarbon radical containing an aromatic nucleus of the benzene andnaphthalene series nuclearly connected to the ether oxygen atom, Arepresents an alkylene group containing more than one carbon atom, a, b,and c are members of the group consisting of alkyl," hydroxyalkyl,aralkyl, and cycloalkyl radicals, d is an anion, and n is an integerless than 3.

11. An ammonium compound of the-formula 1z-- -o-.'\ o.i z in which R isa hydrocarbon radical containing an aromatic nucleus of the benzene andnaphthaalkyl, aralkyl and cycloalkyl radicals, d is an lene seriesnuclearly connected to the ether oxy gen atom, A is an alkylene groupcontaining more than one carbon atom','n is an integer less than 3,

and Z is a nitrogen-containing radical of the group consisting of:

in which a, b, and c are members of the group consisting of alkylhydroxyalkyl, arakyl, and cycloalkyl radicals, e is a saturated radicalwhich forms with N a heterocyclic ring and d is an anion.

HERMAN A. BRUSON.

